Ethyl 2 2-dimethyl-3-(di-n-butylamino)-carbonylcyclobutaneacetate

ABSTRACT

ETHYL 2,2 - DIMETHYL-3(DIS-N-BUTYLAMINO) CARBONYCYCLOBUTANEACETATE, USEFUL AS A PLASTICIZER FO VINYL CHLORIDE RESINS, IS PROVIDED.

United States Patent Oftice 3,644,478 Patented Feb. 22, 1972 Int. Cl.C07c 93/18 U.S. Cl. 260-468 R 1 Claim ABSTRACT OF THE DISCLOSURE Ethyl2,2 dimethyl-3 (di-n-butylamino)carbonylcyclobutaneacetate, useful as aplasticizer for vinyl chloride resins, is provided.

A non-exclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the UnitedStates Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Government of the United States ofAmerica.

This application is a division of United States patent application Ser.No. 683,060, filed Oct. 12, 1967, which, in turn, is a division ofUnited States patent application Ser. No. 529,652, filed Feb. 24, 1966,now United States Pat. No. 3,403,126.

This invention relates to certain compounds which are N-acyl derivativesof symmetrical or asymmetrical secondary amines, to some unique mixturesof the same, and to plastic compositions, the plasticizers component ofwhich is at least one of the compounds or unique mixtures that are thesubject of this invention. More particularly, this invention relates toN,N-disubstituted long-chain aliphatic amides the acyl component ofwhich if saturated is an alkanoic acyl containing from 10 to 18 carbonatoms, and if unsaturated is a monoalkenoic acyl containing from 18 to22 carbon atoms, the amide nitrogen in all cases being the nitrogen atomof a symmetrical or asymmetrical secondary, acyclic or alicyclic amine,said secondary amine being a substituted or unsubstituted acyclic oralicyclic amine.

Specifically this invention relates to symmetrical and asymmetricalN,N-dialkyl amide plasticizers wherein the total number of carbon atomsin the two alkyl groups is from to about 14; to asymmetricalN,N-disubstituted :Lnide plasticizers wherein one of the substituents onthe amide nitrogen is an alkyl group containing from 1 to 4 carbon atomsand the other is a radical chosen from the group consisting of allyl,2,3-epoxypropyl, an alicyclic hydrocarbon radical containing from 5 to12 carbon atoms, benzyl, furfuryl, tetrahydrofurfuryl, 2-acetoxyethyl,Z-methoxyethyl, 2-ethoxyethyl, 2-ethoxypropyl and 2-cyanoethyl; and toasymmetrical N,N-disubstituted amide plasticizers wherein thesubstituents on the amide nitrogen are selected from the group benzyl,cyclohexyl, 2-acetoxyethyl, and Z-cyanoethyl. This invention alsorelates to certain other new amide plasticizers wherein the acylcomponent is derived from epoxyalkanoic or epoxyalkenoic acids, frommonoalkyl esters of pinic acid, from branched chain or neo acids, orfrom long-chain acyl derivatives of short-chain hydroxy acids.

More specifically this invention relates to compounds and mixtures ofcompounds that are good, compatible, solvent-type plasticizers for vinylchloride resins; moreover the compounds and mixtures of this inventionare efiicient, primary, solvent-type plasticizers which can be made fromlow-price fatty acids and which exhibit good compatibility with andimpart not only low volatility loss, resistance to microbial action,excellent low-temperature properties (low brittle points), and stabilityagainst northern light exposure, but also excellent thermal stabilityand antistatic properties to vinyl chloride polymer and c0- polymerresins.

A polyvinyl chloride resin, being a hydrophobic resin, differs fromhydrophilic resins such as cellulose esters, cellulose acetate,cellulose nitrate, and polyvinyl acetal resins in two importantrespects; (1) It tends to develop static charges on its surface due tofrictional forces dur ing manufacture or in everyday use of the plasticproducts. This results in (a) the attraction of dust and lint to theplastic surface, (b) the tendency of one surface or film to adhere toanother, and (c) in general, interference with efficient manufacture andwith consumer acceptance of the finished product. For example, a staticcharge may be developed by the friction of ones clothing on anautomobile plastic seat cover and may even result in a slight butunpleasant spark or shock when the passenger grounds himself or alights.(2) Polyvinyl chloride tends to undergo decompositions on extendedexposure to even moderately elevated temperatures, resulting indarkening and development of discoloration. Dif ferent plasticizersaffect the stability of the polyvinyl chloride to different degrees,some impair and others improve the thermal stability.

Although antistatic properties may be imparted to a surface, at leasttemporarily, by spraying on or coating with a film of an antistaticagent, the antistatic properties imparted have limited permanence andare lost as the film is worn or washed away. It is much moreadvantageous, both from the point of View of permanence and ofeliminating need for the spraying or coating operation, to use anantistatic agent which is a compatible plasticizer, which can be used asthe sole plasticizer, and which when so incorporated in the plasticcompositions still retains and exhibits its antistatic properties.

It is known that N,N-dimethyl-oleamide is an efficient, primary,low-temperature plasticizer for polyvinyl chloride resins. This compoundis also known to possess antistatic properties. We have discovered, inaddition, that when N,N-dimethyl-oleamide is used as the plasticizer inpolyvinyl chloride resin the plasticized stock also has excellentantistatic properties. However, polyvinyl chloride resin plasticizedwith N,N-dimethyl-oleamide exhibits extremely poor thermal stability andtherefore it cannot be used for commercial applications involvingexposure to even moderately elevated tmeperature, such, for example, aswould be encountered in a closed automobile in summer weather.

It was disclosed by Dazzi in US. Pat. 2,875,218 that theN,N,N',N-tetramethyl and N,N,-N',N'-tetra-n-butyl diamides of dimericlinoleic acid are plasticizers for polyvinyl chloride resins. We havefound that N,N,N',N'- tetra-n-butyl diamide of dimeric linoleic acid hasexcel.- lent antistatic properties. However, polyvinyl chloride resinplasticized with this diamide has no antistatic properties and has theadded disadvantage that it exhibits poor thermal stability.

We have made the surprising discovery that when certain of the compoundsof this invention are used as plasticizers for polyvinyl chloride resinsthe plasticized resin possesses both excellent antistatic properties andexcellent thermal stability.

The terms vinyl type resin and vinyl chloride resin are used throughoutthis specification and claims to refer to homopolymers and copolymers ofmonomers containing vinyl chloride in a predominant proportion byweight.

Terms such as compatible, good compatibility, and compatible plasticizerin reference to the plasticizers which are the subject of this inventionare used throughout the specification to refer to plasticizers that showno sign of exudation, migration to the surface, for at least 30 dayswhen the plasticizers are present in the resin in proportion of about 70parts by weight of plasticizer to 100 parts by Weight of resin.

If a resin is plasticized with a compound with which it has only limitedcompatibility, the plasticizer soon exudes or migrates to the surfaceunless the plasticizer is used either in a limited amount or is used inconjunction with a mutual solvent (a compatible auxiliary plasticizer)to obtain adequate compatibility.

It is known in the art that compounds similar to some of those which arethe subject of this invention exhibit reasonably good compatibility forhydrophilic-type resins but in order to obtain adequate flexibility mustbe employed together with a secondary or an auxiliary plasticizer asthose shown, for example, in U.S. Pat. No. 2,339,056.

It would be expected from the recognized compatibility of certaincompounds related to types herein described with polyvinyl acetals(hydrophilic-type resins), that these compounds would be quiteincompatible with polymers of the vinyl chloride type. Certain of theparticular com pounds and compound mixtures herein described are,however, compatible as primary plasticizers with vinyl chloride resinsand, as we note above, they are compatible with the hydrophilic-typeresins as well.

Not only are the particular compounds and mixtures of compounds hereindescribed compatible vinyl-type resin plasticizers, but the instantinvention is considerably broader in that it also contemplates the useof compatible binary, ternary, or multiple component mixtures of N,N-disubstituted amides of mixed saturated, monounsaturated, andpolyunsaturated acids such as can be derived from animal, fish, orvegetable fats and oils such as tallows, white greases, menhaden oil,cottonseed oil, soybean oil, rapeseed oil, safflower oil, Crambeabyssinica seed oil, jojoba oil, parsley seed oil, Limnanthes douglasiiseed oil, palm oil, Vernonia anthelmintz'ca seed oil, castor oil, foots,or from tall oil acids or rosin acids, and other seed oils.

The N-acyl derivatives of this invention decrease in their degree ofcompatibility as the alkyl portion of the acyl group (if saturated)increases in chain length beyond carbon atoms and they are incompatiblewhen the chain length is 17 or more carbon atoms. In general, thecompatibility of a mixture of these N-acyl derivatives of secondaryamines containing a considerable proportion of these less compatible orincompatible N-acyl derivatives can be improved by mixing With acompatible plasticizer or by reducing the proportion of the incompatiblesaturated constituents by such procedures as fractional distillation orfractional crystallization either before or after the amidation step inthe preparation of the N-acyl secondary amine mixture. Similarly, theN-acyl derivatives of this invention decrease in their degree ofcompatibility as the alkyl portion of the acyl group of the N-acylderivative (if unsaturated) increases in unsaturation beyondmonounsaturation. In general, the compatibility of such apolyunsaturated derivative or of a mixture of N-acyl secondary aminessome of which contain such a polyunsaturated acyl can be increased bymixing with a suitable amount of a compatible plasticizer or bydecreasing the proportion of the polyunsaturated constituent either byphysical means, such as fractionation, or by chemical means such asselective hydrogenation, cyanoethylation, halogenation, epoxidation,formylation, maleination, or the like either before or after theamidation step in the preparation of the N-acyl secondary amine orN-mixedacyl secondary amine. The specific component ratio of compatiblecompositions can be established according to 4 the scheme set forth inour copending application Ser. No. 334,685 filed Dec. 10, 1963, forexample.

The preferred N,N-dialkylamides of this invention are those in whicheach of the alkyl substituents on the amide nitrogen contains two ormore carbon atoms and the total number of carbons in the two alkylgroups is from 6 to 14. The preferred asymmetrically N,N-disubstitutedamides of this invention having one alkyl substituent on the amidenitrogen are those in which the alkyl group contains two or more carbonatoms and the total number of carbons in the two substituents is lessthan about 14.

The compounds that are the subject of this invention are convenientlyprepared by reacting the appropriate secondary amine with theappropriate acid, or corresponding acid chloride. In any event, methodsfor preparing compounds such as those described herein are well known tothose skilled in the art of fatty acid chemistry. The details ofindividual preparations are listed in the following operating examples.These examples are set forth by way of illustration and it will beunderstood that the invention is not to be construed as limited to thesecompounds or by the details therein. Analyses are in weight percent.

EXAMPLE 1 N,N-di-n-propyl-ole-amide 20 grams (0.20 mole) ofdi-n-propylamine and 15.6 grams (0.20 mole) of pyridine were dissolvedin ml. of benzene and 59.5 grams (0.20 mole) of oleoyl chloride wereadded dropwise with stirring. After stirring for an additional hour thereaction was filtered, washed successively with dilute hydrochloric acidand Water, and dried over anhydrous sodium sulfate. Free acid wasremoved by percolating the benzene solution through a column ofactivated alumina and eluting the amide with a 1:1 ethanol-benzenemixture. The solvent was then removed by stripping under reducedpressure. Analysis of the product, N,N-di-n-propyl-oleamide (percent):C, 78.82 (theory 78.86); H, 12.98 (theory 12.98); N, 3.64 (theory 3.63).

EXAMPLE 2 N,N-Di-isopropyl-oleamide This compound was prepared by theprocedure of Example 1, from 11.9 grams (0.12 mole) of diisopropylamine,35 grams (0.12 mole) of oleoyl chloride, and 9.2 grams (0.12 mole) ofpyridine. Analysis of the product, N,N-di-isopropyl-oleamide (percent):C, 76.87 (theory 78.76); H, 12.69 (theory 12.96); N, 3.56 (theory 3.83).

EXAMPLE 3 N,N-Di-n-butyl-oleamide A mixture of 27.5 grams (0.21 mole) ofdi-n-butylamine, 40 grams (0.14 mole) of oleic acid, and 20 millilitersof benzene was refluxed in an apparatus equipped with a Dean-Stark trapuntil the evolution of Water ceased. The mixture was diluted with 150ml. of commercial hexane, washed successively with dilute hydrochloricacid and water, and dried over anhydrous sodium sulfate. Free acid wasremoved by percolating the hexane solution through a column of activatedalumina, and eluting the amide with 1:1 hexane-ethanol mixture. Thesolvent was removed by stripping under reduced pressure. Analysis of theproduct, N,N-di-n-butyl-oleamide (percent): C, 78.94 gtlsiggry 79.25);H, 13.16 (theory 13.06); N, 3.44 (theory EXAMPLE 4N,N-Di-sec-butyl-oleamide This compound was prepared by the procedure ofExample 1 from 20 grams (0.15 mole) of di-sec-butylamine, 46.6 grams(0.15 mole) of oleoyl chloride, and 12.3 grams (0.15 mole) of pyridine.Analysis of the product N,N-di-sec-butyl-oleamide (percent): C, 79.04(theory 79.27); H, 13.38 (theory 13.06); N, 2.94 (theory 3.56).

EXAMPLE 5 N,N-Di-isobutyl-oleamide This compound was prepared by theprocedure of Example 1, from grams (0.12 mole) of diisobutylamine, 35grams (0.12 mole) of oleoyl chloride and 9.2 grams (0.12 mole) ofpyridine. Analysis of the product, N,N-diisobutyl-olearnide (percent):C, 78.78 (theory 79.25); H,

13.10 (theory 13.06); N, 3.56 (theory 3.56).

EXAMPLE 6 N,N-Di-n-amyl-oleamide This compound was prepared by procedureof Example 1, from 18.3 grams (0.12 mole) of di-n-amylamine, 35 grams(0.12 mole) of oleoyl chloride and 9.3 grams (0.12 mole) of pyridine.Analysis of the product, N,N-din-amyl-oleamide (percent): C, 79.68(theory 79.81); H, 13.28 (theory 13.15); N, 3.29 (theory 3.32).

EXAMPLE 7 N,N-Di-isoamyl-oleamide This compound was prepared by theprocedure of Example 1, from 19 grams (0.12 mole) of di-isoamylamine,,38.3 grams (0.12 mole) of oleoyl chloride and 9.6 grams (0.12 mole) ofpyridine. Analysis of the product, N,N- di-isoamyl-oleamide (percent):C, 78.90 (theory 78.78); H, 13.14 (theory 13.15); N, 3.25 (theory 3.32).

EXAMPLE 8 N,N-Di-Z-amyl-oleamide This compound was prepared by theprocedure of EX- ample 1, from 19 grams (0.12 mole) of di-2-amylamine,38.3 grams (0.12 mole) of oleoyl chloride and 9.6 grams (0.12 mole) ofpyridine. Analysis of the product, N,N-di- 2-amy1-oleamide (percent): C,79.34 (theory 79.69); H, 12.84 (theory 13.14); N, 3.46 (theory 3.32).

EXAMPLE 9 N,N-Di-n-iexyl-oleamide This compound was prepared by theprocedure of Example 1 from 30 grams (0.16 mole) of di-n-hexylamine,48.7 grams (0.16 mole) of oleoyl chloride and 12.8 grams (0.16 mole) ofpyridine. Analysis of the product, N,N-din-heXyl-oleamide (percent): C,80.11 (theory 80.09); H, 13.45 (theory 13.23); N, 3.15 (theory 3.12).

EXAMPLE 10 N,N-Di-n-heptyl-oleamide This compound was prepared by theprocedure of Example 1 from 21.3 grams (0.10 mole) of di-n-heptylamine,30 grams (0.10 mole) of pyridine. Analysis of the product,N,N-di-n-heptyl-oleamide (percent): C, 80.03 (theory 80.36); H, 13.34(theory 13.31); N, 2.86 (theory 2.93).

EXAMPLE 11 N,N-Di-n-octyl-oleamide This compound was prepared by theprocedure of EX- ample 1, from 24.1 grams (0.10 mole) of di-noctylamine,30 grams (0.10 mole) of oleoyl chloride, and 7.9 grams (0.10 mole) ofpyridine. Analysis of the product, N,N-di-n-octyLoleamide (percent): C,80.58(theory 80.65); H, 13.39 (theory 13.35); N, 2.72 (theory 2.77).

EXAMPLE 12 N,N-Di-2-ethylhexy1-oleamide This compound was prepared bythe procedure of Example 1, from 24.1 grams 0.10 mole) ofdi-2-ethylhexylamine, 30 grams (0.10 mole) of oleoyl chloride and 7.9grams (0.10 mole) of pyridine. Analysis of the product,N,N-di-2-ethylhexyl-oleamide (percent): C, 79.80 (theory 80.65); H,13.25 (theory 13.24); N, 2.90 (theory 2.77).

6 EXAMPLE 13 N,N-Di-n-decyl-oleamide This compound was prepared by theprocedure of EX- ample 1, from 22.7 grams (0.08 mole) ofdi-n-decylamine, 23 grams (0.08 mole) of oleoyl chloride, and 6.1 grams(0.08 mole) of pyridine. Analysis of the product,N,N-di-n-decyl-oleamide (percent): C, 81.01 (theory 81.13); H, 13.37(theory 13.45 N, 2.43 (theory 2.49

EXAMPLE 14 N,N-Di-n-butyl-2-ethylhexanamide This compound was preparedby the procedure of EX- ample 2, from 27.8 grams (0.22 mole) ofdi-n-butylamine, 35 grams (0.22 mole) of Z-ethylhexanoyl chloride, and17.0 grams (0.22 mole) of pyridine. Analysis of the product,N,N-di-n-butyI-Z-ethyIheXanamide (percent): C, 74.97 (theory 75.16), H,12.84 (theory 12.92); N, 5.15 (theory 5.48).

EXAMPLE 15 N,N-Di-n-butyl-neodecanamide This compound was prepared bythe procedure of EX- ample 1, from 22.2 grams (0.17 mole) ofdi-n-butylamine, 40 grams (0.17 mole) of neotridecanoyl chloride and13.6 grams (0.17 mole) of pyridine. Analysis of the product,N,N-di-n-butyl-neotridecanamide (percent): C, 77.27 (theory 77.47); H,13.26 (theory 13.22); N, 4.29 (theory 4.31).

EXAMPLE 17 N,N-Di-n-butyl-palmitamide This compound was prepared by theprocedure of Example 3, from 30.2 grams (0.23 mole) of di-n-butylamineand 40 grams (0.16 mole) of palmitic acid. Analysis of the product,N,N-di-n-butyl-palmitamide (percent): C, 78.75 (theory 78.33); H, 13.72(theory 13.43); N, 4.04 (theory 3.81).

EXAMPLE 18 N,N-Di-n-butyl-stearamide This compound was prepared by theprocedure of EX- ample 3, from 28 grams (0.22 mole) of di-n-butylamineand 40 grams (0.14 mole) of stearic acid. Analysis of the product,N,N-di-n-butyl-stearamide (percent): C, 78.86 (theory 78.85); H, 13.51(theory 13.50); N, 3.49 (theory 3.54).

EXAMPLE 19 N,N-Di-nbutyl-erucamide This compound was prepared by theprocedure of Example 3, from 22.8 grams (0.18 mole) of di-n-butylamine,and 40 grams (0.12 mole) of erucic acid. Analysis of the product,N,N-di-n-butyl-erucamide (percent): C, 79.99 (theory 80.03); H, 13.11(theory 13.22); N, 3.07 (theory 3.09).

EXAMPLE 20 N,N-Di-n-butyl-epoxystearamide This compound was prepared byepoxidation of N,N-din-butyl-oleamide, using meta-chloroperbenzoic acid.The product, N,N-di-n-butyl-epoxystearamide had an oxirane oxygencontent of 3.43%.

7 EXAMPLE 21 N,N-Di-n-butyl-linoleamide This compound was prepared bythe procedure of Example 3, from 27.7 grams (0.21 mole) ofdi-n-butylamine and 40 grams (0.14 mole) of linoleic acid. Analysis ofthe product, N,N-di-n-butyl-linoleamide (percent): C, 79.19 (theory79.65); H, 12.71 (theory 12.61); N, 3.45 (theory 3.58).

EXAMPLE 22 N,N-Di-n-butyl-ricinoleamide 50 Grams (0.16 mole) of methylricinoleate and 41.4 grams (0.32 mole) of di-n-butylamine were refluxedat a temperature such that the methyl alcohol was removed without thedistillation of the di-n-butylamine. The reaction was continued for 36hours after which the product was cooled, dissolved in Skellysolve B,neutralized with dilute aqueous HCl and then water washed. The mixturewas dried over anhydrous sodium sulfate, filtered and then strippedunder reduced pressure. The impure amide was then distilled under 1 mm.pressure. Analysis of the product, N,N-di-n-butyl-ricinoleamide(percent): C, 76.32 (theory 76.15); H, 12.62 (theory 12.45); N, 3,34(theory 3.42).

EXAMPLE 23 N,N-Di-n-butyl-naphthenamide This compound was prepared bythe procedure of Example 3 from 35.7 grams (0.28 mole) ofdi-n-butylamine and 40 grams (0.18 mole) of naphthenic acid (neut.equiv. 217). The product, N,N-di-n-butyl-naphthenamide, had a nitrogencontent of 4.20%.

EXAMPLE 24 N,N,N',N'-Tetra-n-butyldiamide of dimeric linoleic acid Thiscompound was prepared by the procedure of Example 3, from 27.7 grams(0.21 mole) of di-n-butylamine and 40 grams (0.071 mole) of dimericlinoleic acid. The product, the N,N,N',N-tetra-n-butyl diamide ofdimeric linoleic acid, had a nitrogen content of 3.55% (theory 3.58

EXAMPLE 25 Ethyl-2,2-dimethyl-3 (di-n-butylamino)carbonylcyclobutaneacetate This compound was prepared by the procedureof Example 1, from 22.2 grams (0.17 mole) of di-n-butylamine, 40 grams(0.17 mole) of ethyl-2,2-dimethyl-3-chlorocarbonylcyclobutaneacetate,and 13.6 grams (0.17 mole) of pyridine. Analysis of the product,ethyl-2,2-dimethyl-3(din-butylamine)carbonylcyclobutaneacetate(percent): C, 70.11 (theory 70.09); H, 10.90 (theory 11.15); N, 4.14(theory 4.30).

EXAMPLE 26 N,N-Di-n-butyl amide of cottonseed fatty acids This compoundwas prepared by the procedure of Example 3, from 24.6 grams (0.19 mole)of di-n-butylamine and 40 grams (0.15 mole) of cottonseed oil fattyacids. The product, the N,N-di-n-butyl amide of cottonseed fatty acids,had a nitrogen content of 3.26%.

EXAMPLE 27 N,N-Di-n-butylamide of selectively hydrogenated cottonseedfatty acids This compound was prepared by the procedure of Example 3,from 28.2 grams (0.22 mole) of di-n-butylamine and 40 grams (0.14 mole)of selectively hydrogenated cottonseed oil fatty acids. (The selectivelyhydrogenated cottonseed oil fatty acids had an iodine value of 73.2, athiocyanogen value of 68.0, and a neutralization equivalent of 274.) Theproduct, N,N-di-n-butyl amide of selectively hydrogenated cottonseedfatty acids, had a nitrogen content of 3.63%.

8 EXAMPLE 28 N,N-Di-n-butyl amide of rapeseed fatty acids This compoundwas prepared by the procedure of Example 3, from 31.9 grams (0.25 mole)of di-n-butylarnine and 50 grams (0.16 mole) of rapeseed oil fattyacids. The product, the N,N-di-n-butyl amide of rapeseed fatty acids,had a nitrogen content of 3.08%.

EXAMPLE 29 N,NDi-n-butyl amide of Limnanthes douglasii fatty acids Thiscompound was prepared by the procedure of Example 3, from 24.3 grams(0.19 mole) of di-n-butylamine and 40 grams (0.13 mole) of Limnanthesdouglasii seed fatty acids. The product, N,N-di-n-butyl amide ofLimnanthes douglasii fatty acids, had a nitrogen content of 3.23%.

EXAMPLE 30 N,N-Di-n-butyl amide of animal acids This compound wasprepared by the procedure of Example 3, from 27.8 grams (0.22 mole) ofdi-n-butylamine, and 40 grams (0.15 mole) of animal acids. (The animalacids consisted of a mixture of fatty acids, having the followingcomposition: 2% myristic, 26% palmitic, 16% stearic, 48% oleic, and 8%linoleic acids.) The product, N,N-di-n-butyl amide of animal acids, hada nitrogen content of 3.25%.

EXAMPLE 31 N,N-di-n-butyl amide of parsley seed fatty acids Thiscompound was prepared by the procedure of Example 3, from 30.5 grams(0.24 mole) of di-n-butylamine and 50 grams (0.16 moles) of parsley seedoil fatty acids. The product, N,N-di-n-butyl amide of parsley seed fattyacids, had a nitrogen content of 3.08%.

EXAMPLE 32 N-methyl-N-propyl-oleamide This compound was prepared by theprocedure of Example 1, from 15 grams (0.20 mole) ofN-methylpropylamine, 61.8 grams (0.21 mole) of oleoyl chloride and 16.3grams (0.21 mole) of pyridine. Analysis of the product, N methyl Npropyl oleamide (percent): C, 77.57 (theory 78.23); H, 12.91 (theory13.93); N, 3.97 (theory 4.15).

EXAMPLE 33 N-methyl-N-n-butyl-oleamide This compound was prepared by theprocedure of Example 1, from 11.6 grams (0.13 mole) ofN-methylbutylamine, 10.5 grams (0.13 mole) of pyridine and 40 grams(0.13 mole) of oleoyl chloride, analysis of the product,N-methyl-N-n-butyl-oleamide (percent): C, 77.67 (theory 78.75); H, 12.88(theory 12.94); N, 3.88 (theory 4.00).

EXAMPLE 34 N-methyl-N-n-arnyl-oleamide N-methyl-N-n-hexyl-oleamide Thiscompound was prepared by the procedure of Example 1, from 20 grams (0.17mole) of N-methylhexylamine, 52.3 grams (0.17 mole) of oleoyl chlorideand 13.8 grams (0.17 mole) pyridine. Analysis of the product,N-methyl-N-n-hexyl-oleamide (percent): C,

9 78.99 (theory 79.06); H, 13.33 (theory 12.91); N, 3.52 (theory 3.69).

EMMPLE 3 6 N-methyl-N-n-octyl-oleamide This compound was prepared by theprocedure of Example 1, from 20 grams (0.14 mole) of N-methyloctylamine,42.1 grams (0.14 mole) of oleoyl chloride, 11.1 grams (0.14 mole) ofpyridine. Analysis of the product, N-methyl-N-n-octyl-oleamide(percent): C, 78.86 (theory 79.52); H, 13.03 (theory 13.01); N, 3.35(theory 3.44).

EXAMPLE 37 N-methyl-N-n-dodecyl-oleamide This compound was prepared bythe procedure of Example 1, from 20 grams (0.10 mole) of N-methyldodecylamine, 33.1 grams (0.11 mole) of oleoyl chloride and 8.0 grams (0.10mole) ofpyridine. Analysis of the product,N-methyl-N-n-dodecyl-olearnide (percent): C, 80.38 (theory 80.44); H,13.39 (theory 13.19); N, 2.95 (theory 3.03).

EXAMPLE 38 N-methyl-N-allyl-oleamide This compound was prepared by theprocedure of Example 1, from grams (0.21 mole) of N-methylallylamine,63.5 grams (0.21 mole) of oleoyl chloride, and 16.7 grams (0.21 mole) ofpyridine. Analysis of the product, N-methyl-N-allyl-oleamide (percent):C, 77.68 (theory 78.70); H, 12.13 (theory 12.22); N, 4.21 (the-. ory4.18).

EXAMPLE 39 N-butyl-N-n-dodecyl-oleamide This compound was prepared bythe procedure of Example 1, from grams (0.08 mole) ofN-butyldodecylamine, grams (0.08 mole) of oleoyl chloride and 6.6 grams(.08 mole) of pyridine. Analysis of the product,N-butyl-N-n-dodecyl-oleamide (percent): C, 80.55 (theory 82.26); H,13.53 (theory 13.61); N, 2.88 (theory 2.82).

EXAMPLE 40 N-butyl-N-propyl-oleamide This compound was prepared by theprocedure of Example 1, from 20 grams (0.18 mole) of N-butyl-N-propylamine, 54.8 grams (0.18 mole) of oleoyl chloride and 13.7 grams(0.18 mole) of pyridine. Analysis of the productN-butyl-N-propyl-oleamide (percent): C, 78.59 (theory 79.16); H, 13.20(theory 13.03); N, 3.69 (theory 3.69).

EXAMPLE 41 N-butyl N-n-amyl-oleamide This compound was prepared by theprocedure of Example 1, from 20 grams (0.14 mole) of N-butyl-N-amylamine, 44 grams (0.14 mole) of oleoyl chloride, and 11.1 grams (0.14mole) of pyridine. Analysis of the product N-butyl-N-n-amyl-oleamide(percent): C, 79.68 (theory 82.52); H, 12.96 (theory 13.11); N, 3.39(theory 3.44).

EXAMPLE 42 N-methyl-N-cyclopentyl-oleamide This compound was prepared bythe procedure of Example 1, from 15 grams (0.15 mole) ofN-methylcyclopentylamine, 45.5 grams (0.15 mole) of oleoyl chloride, and12 grams (0.15 mole) of pyridine. Analysis of the product,N-methyl-N-cyclopentyloleamide (percent): C, 77.77 (theory 79.54); H,12.29 (theory 12.48); N, 3.84 (theory 3.86).

1 0 EXAMPLE 43 N-ethyLN-cyclohexyl-oleamide This compound was preparedby the procedure of Example 1, from 14.8 grams (0.12 mole) ofN-ethylcyclohexylamine, 9.2 grams (0.12 mole) of pyridine and 35 grams(0.12 mole) of oleoyl chloride. Analysis of the product,N-ethyl-N-cyclohexyl-oleamide (percent): C, 79.26 (theory 79.80); H,12.52 (theory 12.53); N, 3.42 (theory 3.58).

EXAMPLE 44 N-isopropyl-N-cyclohexyl-oleamide This compound was preparedby the procedure of Example 1, from 18.8 grams (0.13 mole) ofN-isopropylcyclohexylamine, 40 grams (0.13 mole) of oleoyl chloride and10.5 grams (0.13 mole) of pyridine. Analysis of the products,N-isopropyl-N-cyclohexyloleamide (percent): C, 79.98 (theory 79.86); H,12.70 (theory 12.57); N, 3.60 (theory 3.45).

EXAMPLE 45 N-methyl-N-cyclooctyl-oleamideN-methyl-N-cyclododecyl-oleamide This compound was prepared by theprocedure of Example 1, from 19 grams (0.10 mole) of-N-methylcyclododecylamine, 31 grams (0.10 mole) of oleoyl chloride, and7.6 grams (0.10 mole) of pyridine. Analysis of the product,N-methyl-N-cyclododecyl-oleamide (percent): C, 80.81 (theory 80.69); H,12.91 (theory 12.91); N, 3.03 (theory 3.04).

EXAMPLE 47 N-Isopropyl-NJ)enZyl-oleamide This compound was prepared bythe procedure of Example 1, from 19.8 grams (0.12 mole) ofN-benzylisopropylamine, 40 grams (0.13 mole) of oleoyl chloride and 10.5grams (0.13 mole) of pyridine. Analysis of the product,N-isopropyl-N-benzyl-oleamide (percent): C, 81.27 (theory 81.22); H,11.61 (theory 11.36); N, 3.39 (theory 3.39).

EXAMPLE 48 N-methyl-N-furfuryl-oleamide This compound was prepared bythe procedure of Example 1, from 14.8 grams (0.13 mole) ofN-methylfurfurylamine, 40 grams (0.13 mole) of oleoyl chloride and 10.5grams (0.13 mole) of pyridine. Analysis of the product,N-methyl-N-furfuryl-oleamide (percent): C, 76.55 (theory 76.68); H,11.17 (theory 10.92); N, 3.81 (theory 3.73).

EXAMPLE 49 N-methyl-N-tetrahydrofurfuryl-oleamide This compound wasprepared by the procedure of Example 1, from 14.8 grams (0.12 mole) ofN-methyltetrahydrofurfurylamine, 9.2 grams (0.12 mole) of pyridine and35 grams (0.12 mole) of oleoyl chloride. Analysis of the product,N-methyl-N-tetrahydrofurfuryloleamide (percent): C, 75.91 (theory75.87); H, 11.83 (theory 12.22); N, 3.59 (theory 3.69).

EXAMPLE 50 N-methyl-N-Z-acetoxyethyl-oleamide Fifty grams (0.17 moles)of methyl oleate was slowly added to a vigorously stirred mixture of13.4 grams (0.18

moles) of N-methylaminoethanol and 2.7 grams (0.12 moles) of metallicsodium dissolved in absolute methanol. The reaction was carried out withcontinued stirring at 65 to 75 C. and at 60 mm. pressure. The reactionwas complete after all the methyl oleate had been added and theevolution of methanol had ceased. To 24 grams (0.71 moles) of theproduct N-oleoyl-N-methylethanolamine which was isolated from thereaction mixture by the addition of a slight excess of glycolic acidfollowed by extraction with hexane, washing and stripping, was added 5.8grams (0.74 moles) of acetyl chloride and 5.6 grams (0.71 moles) ofpyridine. The reaction was carried out in 75 grams of benzene. After thereaction was complete the mixture was filtered, washed successively withdilute hydrochloric acid and water, and finally stripped to remove thebenzene. Analysis of the product *N-methyl-N-Z- acetoxyethyl-oleamide(percent): C, 71.25 (theory 72.33); H, 11.45 (theory 11.36); N, 3.71(theory 3.67).

EXAMPLE 51 N-ethyl-N-Z-acetoxyethyl-oleamide This material was preparedby the procedure of Example 50, substituting N-ethylaminoethanol for N-methylaminoethanol. Analysis of the product, N-ethyl-N-2-acetoxyethyl-oleamide (percent): C, 72.99 (theory 72.83); H, 11.39(theory 11.38); N, 3.35 (theory 3.54).

EXAMPLE 52 N-isopropyl-N-Z-acetoxyethyl-oleamide This compound wasprepared by the procedure of Example 50, substitutingN-isopropylaminoethanol for N-methylaminoethanol. Analysis of theproduct, N-isopropyl-N-2-acetoxyethyl-oleamide (percent): C, 73.91(theory 73.35); H, 11.92 (theory 11.49); N, 2.93 (theory 3.42).

EXAMPLE 53 N-butyl-N-2-acetoxyethyl-oleamide This material was preparedby the procedure of Example 50, substituting N-butylarninoethanol forthe N- methylaminoethanol. The isolated product, N-butyl-N-2-acetoxyethyl-oleamide, gave the following analysis (percent): C, 73.47(theory 73.66); H, 11.63 (theory 11.66); N, 3.44 (theory 3.31).

EXAMPLE 54 'N-ethyl-N-3-eth0xypropyl-oleamide This compound was preparedby the procedure of Example 1, from 25 grams (0.19 mole) ofN-(3-ethoxypropyl)ethylamine, 57.2 grams (0.19 mole) of oleoyl chloride,and 15.1 grams 0.19 mole) of pyridine. Analysis of the product,N-ethyl-N-3-ethoxypropyl-oleamide (.percent): C, 75.96 (theory 75.83);H, 12.67 (theory 12.48); N, 3.56 (theory 3.54).

EXAMPLE 5 5 N-cyclohexyl-N-2-acetoxyethyl-oleamide This compound wasprepared by the procedure of Example 50, substitutingN-cyclohexylaminoethyl for N- methylaminoethanol. Analysis of theproduct, N-cyclohexyl-N-2-acetoxyethyl-oleamide (percent): C, 74.65(theory 74.73); H, 11.43 (theory 11.45); N, 3.30 (theory 3.12).

EXAMPLE 56 N-Cyclohexyl-N-Z-cyanoethyl-oleamide This compound wasprepared by the procedure of Example 1, from 20.5 grams (0.13 mole) ofN-(2-cyanoethyl) cyclohexylamine, 40 grams (0.13 mole) of oleoylchloride and 10.2 grams (0.13 mole) of pyridine. Analysis of theproduct, N-cyclohexyl-N-2-cyanoethyl-oleamide (percent): C, 78.08(theory 77.00); H, 11.77 (theory 11.29); N, 6.90 (theory 7.19).

12 EXAMPLE 5';

N-Benzyl-N-2-acetoxyethyl-oleamide This compound was prepared by theprocedure of Example 50, substituting N-benzylaminoethanol for N-methylaminoethanol. Analysis of the product N-benzyl- N 2 acetoxyoleamide (percent): C, 75.67 (theory 76.15); H, 10.27 (theory 10.28); N,2.88 (theory 3.06).

EXAMPLE 5 8 N,N-Bis [2- 3-carbobutoxypropionyloxy) ethyl] -oleamide To37 grams (0.10 mole) of N,N-bis(2-hydroxyethyl) oleamide was addeddropwise with stirring 46 grams (0.22 mole) of3-chloroformylbutylpropionate in the presence of 20 grams (0.25 mole) ofpyridine. After reacting for an additional hour the product wasdissolved in hexane, filtered, washed successively with aqueoushydrochloric acid and Water, and dried over anhydrous sodium sulfate.The solvent was removed by stripping under reduced pressure. Analysis ofthe product, N,N-bis [2 (3 carbobutoxypropionyloxy)ethyl] oleamide(percent): C, 67.90 (theory 66.90); H, 10.24 (theory 9.90); N, 2.08(theory 2.06).

EXAMPLE 59 N,N-Bis [2-(3-carbohexanoxypropionyloxy)ethyl] oleamide Thiscompound was prepared by the procedure of Example 58, from 36.9 grams(0.10 mole) of N,N-bis(2- hydroxyethyl)oleamide, 48 grams (0.22 mole) of3- chloroformylhexylpropionate and 20 grams (0.25 mole) of pyridine.Analysis of the product,N,N-bis[2-(3-carbohexanoxypropionyloxy)ethyl]oleamide (percent): C,69.05 (theory 68.40); H, 10.32 (theory 10.19); N, 2.06 (theory 1.91).

EXAMPLE 60 N,N-Di-n-butyl-2-(o1eoyloxy)propionamide 153.2 grams (1.19moles) of di-n-butylamine and 70 grams (0.59 mole) of ethyl lactate wererefluxed for 16 hours at a temperature just sufiicient to liberate theethanol formed. After the excess dibutylamine had been stripped underreduced pressure, the product N-lactoyldibutyl amine was obtained byvacuum distillation, dissolving in ether and percolating through acolumn of activated alumina. The solvent was then removed by strippingunder reduced pressure. To 30 grams (0.15 mole) of the productN-lactoyldibutylamine was added, 11.8 grams (0.15 mole) of pyridine, and48.9 grams (0.16 mole) of oleoyl chloride. The reaction was carried outin 100 ml. of benzene. The reaction product was isolated from thismixture by filtration, followed by washing with dilute hydrochloric acidand water, and finally stripped to remove the benzene. Analysis of theproduct N,N di n butyl 2 (oleoyloxy)propionamide (percent): C, 73.39(theory 74.71); H, 11.78 (theory 11.81); N, 2.99 (theory 3.01).

Portions of the products prepared according to the examples set forthabove were evaluated as primary, solvent-type plasticizers forvinyl-type resins by the following procedures:

(1) Incorporating the plasticizer in a vinyl chloridevinyl acetatecopolymer (Vinylite VYDR) a copolymer consisting of vinyl chloride and5% vinyl acetate.

(2) Incorporating the plasticizer in a polyvinyl chloride homopolymer(Geon 101).

In either method, the following standard formulation is used, percentbeing by weight: 63.5% homopolymer (or copolymer), 35.0% plasticizer,0.5% stearic acid, and, as stabilizer, 1.0% basic lead carbonate.

The formulation for each sample is then milled, molded, and then testedfor: (a) tensile strength (p.s.i.); (b) modulus (p.s.i.); (c) elongation(percent);

miny thirty minutes the specimen is removed from the oven, cooled,

ompositings are cized comthickness, is laid on alumina forced s of en inTable Antistatic rating 2 excellent antistatic properties and are rated0. Those i in in a y mean del No. ber

percent of ii" initial re- Brittle Volitilpoint, ity loss, Compat- 0.percent ibility 1 z A 3 x 4-inch sheet of the milled plast and placed ona standard white backal reflectance of the untreated sample 100%Elongamodulus, tion, p.s.i. p.s.i. percent;

origin ti rated 3, 2, and-1 are intermediate in antistatic effect. Thenylon fabric is changed after each test. The ra reported in Table I.

The relative thermal stabilities of the plasticized compositions weredetermined by the following test procedure position, to mils foil andsubjected to a temperature of 176 C draft oven for incremental exposureperiods of u-tes. Ever ground. The reflectance is then determined b aphotoelectric reflectometer (we used Mo of the Photovolt Corp.)employing the am directional reflectance. The loss in reflectance is ameasure of degree of discoloration. The results, giv II, show the lossin reflectance expressed as ons retaining the greatest percentage of thefiectance value, i.e., those exhibiting the smallest reflectance lossfor a given exposure period, have the greatest thermal stability.

Tensile strength 3,644,478 13 (d) brittle point C.); (e) volatility lossin percent; and, (f) compatibility. Portions of the milled samples d forthermal sta- The results of the above tests are then compared with 5control results obtained when a standard plasticizer such theproportions used. The sample 10 tible if the molded stock showed anyevidence of exudation or migration to the surface during a shelf storageof 30 days.

The antistatic properties of the plasticized resins were determined bythe following procedure: A sheet of the 1 milled plastic composition isstroked ten times in the same direction with unsoiled nylon fabrictautly draped over the bristles of a scrubbing brush and is then'care--inch deep Petri ining a layer of finely powdered cigar ashes. 20

attracting and holding the greatest quantity of ash have poor antistaticproperties and are given a rating of 4. Conversely those attracting noash have TABLE I Plasticizer were tested for antistatic properties anbility.

as di-2-ethylhexylphthalate (DOP) is used. These results are summarizedin Tables I and II. In Table I, C denotes compatibility and I denotesincompatibility as primary plasticizers in was rated as incompa fullyplaced so as to fully cover a /2 dish conta Those samplesCCCCCCCCCCCIIICCCC CCIICCC C CCCCCCCCCCICCCCCCCCCCCC CCCCCICCC nnnmnnwwman nmwmnnna an an anennanewn I a n a a a a v 1 I l I l l n n l n o a aI s I a o I a u e 1 l l a u a v e s I a u 2112201 00 mm90000 805 210002211110 h 0 000 0110 1101000011 0 0 0 00 000000000000000000000050000000 0 3302134682 m 5 354565 0 0 05 93358577861m926 24 10 0 3aas aaalzim maaaaszss ans 43 233aass. .a2a saanasaannaannnnnnannn000 0 nnn m n ddd m d mmm d m 000000000 00000000 8000 00 00000000000 000 672240483 8706429 186 12 527545590930 40004.0000000000000000 v 1 "WWWm 4 34 6544121245 M5M%%EWWWHMNW%%NHW%MHM 111111111 11121111 121 1 1-LLLLLLLLLLL LLLLLL LLLLLLLLLLLL LL nloride homopolymer instead ofcopolymer resin (V inylite VYD R). 4 A rating of zero was obtained foreac of these plasticized resin samples after a very thin film of thespecific plastlcizer used as planticrzer had been applied to the surfaceof the plasticized resin.

Percent loss in reflectance min. 0.0 61.7 74.8 97.3

TABLE II Plastlclzer N,N-dimethy1-oleamlde Example No.:

Swamp 5 07 5 7 5 566597wl 799 210 mins.

mins. mins. mm s. mins.

Percent loss in reflectance mms.

0 30 min. mins.

Examiner a plastic composition of the following formulation, percentbeing by weight: 62.7% Vinylite VYD'R, 34.6% plasticizer, 0.5% stearicacid, 2% polymeric dibutyl tin mercaptide (Awastab T360), and 0.2%alkylarylphosphite (Avastab CH300).

' TABLE III Plastlcizer N,N-dimethyl-oleamide 1 N,N-di-n-propyl-oleamide3-.- N,N-di-n-butyl-0leamide.-

We claim: 1. Ethyl 2,2 dimethyl3(di-n-butylamino)carbonylcyclobutaneacetate.

References Cited UNITED STATES PATENTS 3,031,499 4/1962 Hedrick 260-514OTHER REFERENCES Mod et al., I. Am. Oil Chemists Society, 42, 941 (1965LORRAINE A. WEINBERGER, Primary R. GERSTL, Assistant Examiner 24...N,N,N,N-tetra-n-butyl diamide of dimerized linoleic acid- 54..N-ethyl-N-3-ethoxypropyl-oleamide N.N-di-n-butyl-2-oleoyloxy) propiona20 {N,N-d1-n-buty1-epoxystearamide DOP 7 (control)...

1 Commercial product.

The improved thermal stability of the polyvinyl chloride resinplasticized with N,N-n-dibutyl oleamide over Example No.:

2 Di-2-ethylhexyl phthalate.

that with N,N-dimethyl oleamide is shown more emphati- 25 cally when ahighly cfficient but much more expensive stabilizer formulation is usedinstead of basic lead carbonate, as shown by the thermal stability datain Table III for

